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2K views29 pages31 Intermolecular Forces and PES
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Mohit KambojCopyright
© © All Rights Reserved
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Available Formats
Download as PDF or read online on Scribd
INTERMOLECULAR FORCES
AND POTENTIAL ENERGY SURFACES
—__ ee SS
SYLLABUS (4 Lecturers)
Jonic, dipolar and van Der Waals interactions. Equations of state of real gases and critical
Phenomena. Potential energy surfaces of H3, HF and HCN and trajectories on these surfaces.
3.1 INTRODUCTION
forces present betwer a ubstances are called intermolecular)
| forces These forces are present in all kinds of molecules. These weak attractive forces are
present for all the states of matter and determine their structural and physical properties. These
forces are present in ever such as H>, Cly, CHy etc... since all these
substances can be liquified. Even the inert gases such as He, Ne, Ar. etc Possess intermolecular
force because they can also be liquified, and some weak forces must be o
molecules
perative among the
The existence of these forces among the non-polar molecules in their liquid and solid
states was first proposed by the Dutch scientist J.D Van der Waals. Interaction between various
molecules leads to intra-molecular forces, which affect the physical as well as chemical
Properties of the comp. - Along with intermolecular forces, we shall take up the study of
Potential energy surfaces in this chapter.
3.2__ TYPES OF INTERACTION FORCES
It is completely established that forces of attraction exist between polar as well as non-
Polar molecules. These intermolecular forces called Cohesive forces or Van der Waals ‘forces
originate from two types of interactions. namely (i) Dipole - Dipole Interactions and (ii) Induced
Dipole - Induced Dipole Interactions
(147) 14s CONCEPTUAL ENGINEERING CHEMISTRY
The following types of intermolecular forces exists between the molecules of different
substances:
1. Dipole-dipole interaction
2. Induced dipole-induced dipole
3. Ion-dipole
4. Ton-induced dipole
5
Instantancous dipole-instantancous induced dipole forces (or dispersion forces)
It may be noted that the term Van der Waals forces refer to dipole-dipole, dipole-
induced dipole and dispersion forces.
1. Dipole-dipole interaction: These are second strongest intermolecular forces. These
forces exit between permanent dipoles. The dipole tend to align with oppositely charged ends
directed at cach other As permanent dipoles exist only in polar compounds, so these interaction
occur only in polar compounds, e.g. acetone and dichloromethane, These forces weaken even
more rapidly as the distance increases as compared to an ion-dipole interaction
{<< BDD E>
S288 2axRe
LDL DL DED Naa
Solid Liquid
Fig. 3.4
These forces are also called Keesom forces as these were first studied by Keesom
(1912). He termed this effect as orientation effect.
2. Induced dipole-Induced dipole Interaction. (London Forces or Dispersion
Forces): As we know, the Van der Waals forces exist even in nonpolar molecules such as 0»
and Ny and also in inert gases such as He, Ne, Ar, etc. This attraction is clear from the
condensation of these gases into liquids at sufficiently high pressures and low temperatures.
In 1930, F, London provided a satisfactory explanation for the existence of forces of
attraction between non-polar molecules on the basis of quantum mechanics. According to him,
electrons of a neutral molecule keep on oscillating with respect to the nuclei of the atoms. As @
result, at a given instant, positive charge may be concentrated in one space and negative charge
in another space of the same molecule. Thus, a non-polar molecule may become polarised
for a little while, this polarised molecule may induce a dipole moment in a neighbouring molecule
with anti-parallel orticntation, as shown in Fig. 3.2
The electrostatic forces of -
attraction between induced dipoles =) a)
and the original dipoles (due to a
electron oscillation) are known as Original Original dipole duc to Induced dipole
the London forces. These forces molecule electron oscillation
Fig. 3.2. Origin of cohesive forces in non-polar molecu?
i INTERMOLECULAR FORCES AND POTENTIAL ENERGY SURFACES dad
are also called dispersion forces because the well known phenomenon of dispersion of light is
also related with these dipoles. The Van der Waal’s attraction in nonpolar molecules is thus
exclusively due to the London forces
The average interaction energy in this case is given by
Interaction energy, $(r)
where C is a constant, depending upon the ionisation energy of the two molecules.
Nature of the Van der Waals Interactions.
Though the Van der Waals constants a and 6 take into consideration the effect of
attractive interactions in gaseous molecules, the exact nature of these interactions has to be
understand, Since molecules are composed of positively charged nuclei and negatively charged
electrons, whenever any two molecules come closer, interactions occur between the charge
clouds of the nuclei and the electrons of the two molecules. At relatively large intermolecular
distances, the attractive forces originating from attraction between electrons and atomic nuclei
operate between the two molecules. At very small distances, however, the molecules strongly
repel each other, the repulsion arising from the interaction between the similarly charged electron
clouds. Thus, we expect the intermolecular potential energy to be composed of the long range
attractive term and the short range repulsive term.
3. Ion-dipole forces: These are the strongest inter-nuclear forces. These occur
between the ions formed by dissolving the ionic compound in polar solvents. The polar solvent
is generally water but it can also include organic salts dissolved in polar organic compound, ¢.g
[Et,N]Br in acetone. The negative end of the dipole will be attracted to positive ions and vice
versa.
The magnitude of the interaction between these dipoles and ions depends upon the ionic
charges and size of dipoles. These forces sharply decrease with increasing distance. Thus,
they act over very short distance only.
Cow CD Cea €>
Fig. 3.3,
4. Ion-induced dipole interactions: These interactions occur between an ion and
the induced dipole, for example dissolving benzene in acetone. This occurs when the iom
approaches towards non-polar molecule, the symmetrical distribution of non-polar molecule 150 CONCEPTUAL ENGINEERING CHEMISTRY
gets distorted because the electrons on the non-polar molecules are attracted to the positive
end of the dipole and repelled by the negative end of the dipole. The interaction lasts as long as
the polar molecule is near the non-polar molecule. The formation of induced dipole depends
upon the charge on the ion and polarizability of the atom or molecule. As a result, these forces
are weak forces and effective only at short range
— <>
Polar Non-polar Polar Molecules with
molecule molecule molecule induced dipole
Fig.3.4
5, Instantaneous dipole- instantaneous induced dipole forces: Let us try to
understand the formation of instantaneous dipole. When two noble gas atoms are very close to
each other, each atom is uncharged because the electron distribution around the nucleus is
symmetrical. However, due to motion of electrons, itis possible that for the fraction of time, electron
distribution is not symmetrical because of the distortion of the electron cloud. As a result, a smatl
temporary dipole is formed called induced or instantaneous dipole. The instant or induced
dipole further distorts the electron cloud of neighbouring atom as shown below in Fig. 3.5
Permanent dipole Non-polar
(a polar molecule) molecule
. =
s+—s stos
Permanent dipole Induced dipole ina
(a polar molecule) non-polar molecule
Fig. 3.5. Interaction between permanent dipole and induced dipole
The attraction that occurs between induced dipole is called induced dipole-induced
dipole interaction. As the magnitude of charges developed is very small, these forces can
operate over the shortest distance of all forces and hence are weakest forces. The strength of
these forces depends upon
(i) size of molecul, i.c. its molecular mass,
(i) number of electrons present in the molecule, and
(ii) molecular structure. INTERMOLECULAR FORCES AND POTENTIAL ENERGY SURFACES i
The larger the size, the higher the number of electrons present in the molecule or an
atom more easily, the atom can be polarized (i.e. easily undergo distortion of electron cloud)
and greater will be the strength of these forces. So, larger the size of the molecule of an atom,
Breater will be the strength of these forces and vice versa
3.3 IDEAL AND REAL GASES
1, Ideal Gases
Gases which obey gas equation PV = RT rigidly for all values of temperature T
and pressure P are called ideal or perfect gases. Thus an ideal or perfect gas is one
which rigidly obeys Boyle's and Charles law at all values of temperature and pressure
Characteristics of an ideal gas may be summarised as:
(i) The product of pressure and volume of a given mass of an ideal gas at constant
temperature should be constant, i.c., if product PV is plotted against pressure P at
constant temperaturo, the curve obtained should be a straight line parallel to the pressure
axis (Boyle's law).
PV
(ii), The compressibility factor (z = 5) of an ideal gas should be unity i.e. PV =n RT
(Gas equation),
(iii) If at a constant pressure, the temperature is reduced, the volume should get reduced
uniformly and become zero at -273°C or zero Kelvin (Charles Law).
(iv) If a gas. is allowed to expand without doing any external work, it should show no
thermal effect (No force of attraction between the molecules)
(v) At constant temperature if pressure is doubled, the volume should reduce to half (Boyle's
law).
(vi) According to Avogadro's law, one mole of every gas should occupy 22.4 litres at N.T.P.
(0°C and 1 atm). Experiments show that this is true only approximately because the
actual value for different gases does not come out to be the same (Avogadro's law)
If we study, However, the actual behaviour of the gases, we notice that ho gas is ideal
or perfect in this sense although some gases approach perfection as the temperature
rises above their boiling points.
Thus, an ideal or perfect gas is only hypothetical. It has been observed that at high
Pressures and low temperatures gases do not obey the gas laws, However, at low pressures
and high temperatures they obey the gas laws to a fair degree of approximation. Such gases
are, therefore, known as real gases.
2. Real Gases
Real gas is one which obeys the gas laws fairly well under low pressure and high
femperature, It means all gases are real gases, but they show deviation from ideal behaviour.
‘The deviations are more pronounced as the pressure is increased or the temperature is decreased
Further in case of real gases it is not possible to reduce uniformly the volume of a gas to zero 162 CONCEPTUAL ENGINEERING CHEMISTRY
at -273°C, as all real gases liquefy when sufficiently cooled, Real gases like Oy, Hy, No, ete
which are difficult to be liquefied differ from an ideal gas to a greater extent than lik:
© NH;,
$05, CO, ete., which can be easily liqueficd. Helium shows an ideal gas behaviour to soy’
some
extent
We know that no gas is ideal or perfect, the gas equation is obeyed as an approximation
by a real gas at low pressure and high temperature, while at high pressure and low temperature
there is much deviation from this ideal behaviour.
3.4 DEVIATIONS OF REAL GASES FROM GAS LAW (BOYLE'S Law)
1, Effect of Pressure
)
1
The plots of PV versus P for various
gases at 0°C are depicted in Fig. 3.6. For an
ideal gas, the plot should be a straight line
parallel to pressure axis. Such a plot is
indicated by a dotted line. It is clear from
the various plots that all gases deviate
considerably from the ideal gas behaviour
and the product PV does not remain constant P (Atmosphere) ——>
with increasing pressure. Only in the limit Fig. 3.6. PV Vs P plot (variation of PV with P)
of zero pressure, all gases are behavirig for various gases at 0°C
ideally.
ole
Pyv—
Se ee
(Litre Aun. deg
0 200° 400 600-800-1000
A close examination of Fig. 3.6 reveals that all the curves can be classified into two
types:
Type 1: Here the curves start ascending at once from the value of PV and the value of
PV increases continuously with increasing pressure. This is true in case of gases having smaller
molecules, ¢.g., Hp. He, ete.
‘Type 2: Here the curves show a decrease in PV in the beginning, passes through a
minimum and then begins to increase with increasing pressure. This is true in case of gases
having larger molecules e.g.; Oy, N>, CO, etc
Above 400 atmospheres, the product of PV increases with the increase in pressure for
all gases.
Compressibility Factor
To show both the deviations more clearly, a quantity, called compressibility factor (Z) is
used which, is defined as:
Zee
RT
where V is the volume occupied by one mole of the gas at a given temperature T and
pressure P. INTERMOLECULAR FORCES AND POTENTIAL ENERGY SURFACES =
For an ideal gas, Z=1 and is independent of pressure and temperature.
For a real gas, Z is a function of both temperature and pressure and its value varies.
The amount by which the actual factor differs from a value of unity gives measure of
deviation from the ideal behaviour.
g
Since (PV)i4eq) = RT 314
by py i
RT (PV)igeai Bos
So compressibility factor is a measure of deviation 4
from ideality. z
. S 0 100 200 300
Fig. 3.7 shows a plot of Z versus P for some gases P (Atmosphere) —>
at 0°C. For Ha, the value of Z continuously increases but Fig. 3.7 Zvs.P curves for
for No, CH, and CO>, Z first decreases and then increases various gases at 0°C
quite rapidly with increasing pressure.
It has been found that for those gases which can be easily liquefied, Z decreases
sharply below the value of unity at low pressure. Since carbon dioxide is a gas which can be
more easily liquefied than nitrogen and methane, therefore, the dip in value of Z is much more
Pronounced in carban dioxide and, persists over a range of pressures. But as hydrogen gas
cannot be easily liquefied, its curve does not show any dip in the value of Z with increasing
pressure.
Effect of temperature
If a plot of Z (compressibility) or
relative PV versus P is constructed for a gas at
several temperatures, it is fund that as the
temperature decreases, the dip in the curve is
more pronounced.
b
S
Fig.3.8 shows various curves of Z (or
relative PV) versus P for nitrogen at various
temperatures,
a
All the curves start with Z = | at P= 0
and value of Z varies from unity as pressure
increases in a manner dependent on 12)
temperature. As the temperature increases, the
minimum in the curve (dip) becomes smaller
and shifts towards lower pressure
PV (Relative) —>
z
1.0)
0 é
0 200 400 600 3800 1000
However, a temperature is reached at Pressure in Atmospheres —>
which Z remains close to unity over an
i ig. 3. tion of Z (relative PV) with P
appreciable range of pressure. Fig. 3.8. Variation of Z (!
for nitrogen at various temperatures a
184 CONCEPTUAL ENGINEERING CHEMistRy
It is seen that in case of nitrogen when PV values are plotted against Pressure at
differes
nt temperatures, the shape of PV curve changes with temperature. In eneral the
deviations are greater at higher pressures and near the te
is also observed that nitrogen gas behaves Lik
-mperature of liquefaction. Further ip
whereas at lower temperatures it behaves like
e hydrogen gas at higher temperatures
CO,
An examination of the Fig. 3.8 also reveals that at 50°
constant and is close to the value of the ideal gas for an appreciable Tange of pressure. In fact
upto 100 atmospheres pressure, the compressibility factor (Z), changes from 1.0 to 1.02 Beyond
100 atm. the value of Z increases rapidly and attains values much greater than |
The temperature at which a real gas obeys the ideal gas law over an appreciable
range of pressure is known as the Boyle's temperature or the Boyle point. It is so named
because at this temperature Boyle's law is obeyed over a range of pressures, Obviously about
the Boyles temperature, a gas shows Positive deviation only.
‘C the value of PV remains
For every gas when the temperature is below
or PV will first decrease with increasing pressure, pass through a minimum and then increase
continuously, But ifthe temperature is above the Boyle's point, Z or PV increases sharply, with
increasing pressure and the values of Z-are higher than unity.
the Boyle’s temperature, the value of Z
The Boyle’s temperature is different for different gases. Boyle's temperature for
hydrogen and helium are ~165°C and ~240°C respectively: Hydrogen gas obeys Boyle’s law at
~165°C for an appreciable range of pressure. Below this temperature plot of PV versus P will
first show a fall and then a rise with the increase of Pressure. Obviously, above the Boyle’s
temperature all gases show positive deviations
From the above observations the following three points are evident
(i) At low pressures, the values of PV for all
gases except hydrogen, helium and neon,
are lower than those expected of an ideal g ;
as.
(ii) At high pressures, the value of PV for all gases including Hy, He, Ne, ete., are higher
than those expected of an ideal gas.
Effect of temperature: At a particular Pressure the deviation of a gas from ideal
behaviour is more pronounced at low temperature. The lower the temperature, the
greater are the deviations.
3.5 CAUSES OF THE DERIVATIONS FROM IDEAL BEHAVIOUR
The failure of the ideal gas equation PV=RT over an extensive range of temperatures
and pressures has been explained by Van der Waal's to be due to the following two faulty
assumptions made in the kinetic theory:
(i) The actual volume occupied by the gas molecules is negligible as compared to the
total volume of the gas.
(ii) The molecules exert no inter-molecular attraction among themselves, INTERMOLECULAR FORCES AND POTENTIAL ENERGY SURFACES ae
Both these assumptions are not true, particularly at low temperature and high pressure
So, necessary correction to the ideal gas equation should be made.
3.6 VAN DER WAALS’ EQUATION (REDUCED EQUATION OF STATE)
(EQUATION OF STATE FOR REAL GASES)
Van der Waals’ deduced a modified gas equation by making following necessary
corrections to the gas equation PV = RT.
1. Volume correction
The assumption that actual volume of the molecules is negligible, does not introduce
any appreciable error at low pressures. At high pressure when the molecules are quite close
together, the volume occupied by the molecules themselves becomes considerable fraction of
the total volume occupied by the gas.
According to Van der Waal the actual free space available inside the vessel for the
movement of the molecules is not V, the volume of the container, but (V-b), where ‘b’ is the
effective volume of the molecules. It can easily be shown that effective volume of molecules
in motion is equal to about 4 times the actual volume of molecules at rest. The effective volume
(6) is also called co-volume or excluded :
volume
Let us consider two molecules
approaching each other. Let 8 and r
represent the diameter and the radius of
each molecule. The molecules cannot
approach more closely than the distance 8
as shown in Fig. 3.9. It is because the
molecules are impenetrable. It is clear from
the figure that within a sphere of radiug 8
(=2r), no volume will be occupied by this
pair of molecules, Thus:
“~— Excluded volume
of radius 5 = 2
Fig. 3.9 Excluded volume of a pair of
molecule
. 4
The excluded volume per pair of molecules = $x(2r? = (xr)
So excluded volume for a single molecule - 8 (3+) =4V,
. 2\3 :
where V,,, is the volume occupied by a single molecule,
Thus the excluded volume (b) for a mole of a gas is given as :
|
| 156 CONCEPTUAL ENGINEERING CHEMISTRY
where N being the Avogadro's number.
Hence. the corrected volume = (V-b)
where 6 is the volume to be excluded which is four times the actual volume of the
molecules and it is a characteristic constant for each gas.
2. Attraction correction — Pressure correction
The assumption that molecules exert no appreciable intermolecular attraction is not
justified especially at high pressure when the molecules are quite close together.
Consider particles A and B in the gas Fig. 3.10. The net force of intermolecular attraction
on particle “A” situated in the interior of the gas is nil, because it is surrounded by moleculles
which are equally distributed in opposite directions, thereby the attractions on all sides are
mutually cancelled.
‘Net Force of Net Attraction
Attraction is NIL Force Inward
* 4
Fig. 3.10. Molecular attraction
However, molecule “B" just near the boundary
which is about to strike the wall. is subjected to a net
inward force of attraction or pull due to the interior
molecules, So, when a molecule is about to strike the
wall, this inward pull act, so as to reduce the force
exerted by the impact and consequently the measured
pressure P is less than the ideal pressure, i.e. when
no attraction were there. The observed pressure is thus less than that would be expected from
the Kinetic theory. This will tend to make PV less than RT and so will tend to cause a negative
or under perfect deviation. Hence, a correction term p, should be added to P to to get ideal
pressure.
Ideal pressure = P +p,
The inward force, p, exerted on molecules about to strike the walls of the vessel is
proportional to:
(i) The number of molecules striking the wall at any given instant, which ix proportional
to the density of the gas.
(i) The number of molecules in the interior which are attracting the striking molecules,
which is also proportion to the density of the gas.
p, « d*
But density =
volume INTERMOLECULAR FORCES AND POTENTIAL ENERGY SURFACES ar
a
ve
where ‘a’ is a proportionality constant. called co-effictent of attraction.
Hence, ideal pressure =
Incorporating the volume correction and attraction correction (or pressure correction)
in the gas equation, we get
(vp) [P+
This modified gas equation is called the Van der Waals’ Equation of state as it was first
established by J.D. Van der Waals” ~ a Dutch chemist in 1873. It represents the behaviour of
real gases over a wide range of temperature and pressure for one mole of gases.
If there are n moles of the gas occupying volume V, then the effective volume of the
molecules is given by nb and the actual free space available inside the vessel for the movement
of the molecules is then V-nb.
The pressure correction p, xn? d?
Therefore, the Van der Waal’s equation for n moles of a gas will be
[r+ ma) (V-nb)=nRT GB.2)
3.6.1. Units of Van der Waals’ Constants
The units for Van der Waals” constants a and b depends on the units in which P and V
are expressed
From equation P,
on Pressure x (Volume
(moles)”
If pressure is expressed in atmospheres and volume in litres, a will be expressed in atm.
litre? mole?
Go 168 CONCEPTUAL ENGINEERING CHEMistRy
In ST Units: Now volume correction for » moles of a gas is 7b
Volume correction = nb
p= Nolume
n
In SI Units: If volume is expressed in litres, the units of b are litre mol !.
3.6.2 Significance of Vander Wall’s Constant
The gases such as CO,, NH, HCI which can be easily liquefied, have high values of
Van der Waals’ constant @ and 6 and show maximum departure from the ideal gas equation.
The Van der Waals’ constant ‘a’ is a measure of strength of the Van der Waals’ force
between the molecules of the gas. Greater the magnitude of a, stronger are the Van der Waals"
forces. The greater the magnitude of these, forces, i.e., a, greater is the ease with which gas
can be liquefied.
The Van der Waal’s constant *b” represents effective volume of gas molecules, It has
been observed that its value remains constant over a wide range of temperature and pressure
for a gas. This shows that gas molecules are incompressible
3.7 EXPLANATION OF BEHAVIOUR OF REAL GASES ON THE BASIS
OF VAN DER WAAL’S EQUATION
a
( . 4] (v-b)= RT Van der Wall's equation of state.
or PV+S pp RT
vi
ab
Neglecting yea product of two very small quantities, we get
or PV-Pb+2 =RT=P'V! (3.3)
where P’ and V’ are the ideal pressure and ideal volume of the gas respectively.
(i) At low pressure: At lower pressure the gas has a large volume and volume taken
up by the molecules is relatively unimportant. Small addition of pressure due to mutual attraction
plays an important part while b is negligible as compared to the large total volume V. The factor
we therefore, overweight Pb ic, 4>Ps
Let “Pb =Z, positive quantity
v
From equation (3.1), we get INTERMOLECULAR FORCES AND POTENTIAL ENERGY SURFACES -
PV4Z = RT = PIV"
PV =RT-Z=P'V'-
¢., the observed PV is less than P' V'.
The observed product PV at low pressure is less than P’ V’, product of pressure and
volume if the gases were ideal. Thus the intermolecular attractive forces cause a negative or
under perfect deviation.
At low pressures, therefore, PV decreases with increase in pressure in case or N>, O7
and CO). ete.
(ii) At high pressure: When the pressure is high, the volume is small and small volume
occupied by molecules themselves cannot be neglected, whereas in comparison with the high
pressure, small addition of pressure due to mutual attraction is negligible. Hence Pb over weights
@ a
a Pb> 2
77 be: Pb>
, anegative quantity
PV+(-y)=P'V! or PV-y=P'V’
PV =P'Vit+y
i.c., the observed PV is greater than the value expected from an ideal gas. The volume
occupied by the gas molecules cause a positive or over perfect deviation.
This explains the fact that PV, after reaching a minimum, increases with further increase
in pressure.
(iii) At extremely low pressures and high temperatures: When P is very small, V
will be very large. In this case both the correction terms -“ and 4, in the Van der Waals”
Vv
equation are negligibly small in comparison to P and V and the equation reduces to PV = RT the
equation for an ideal gas. Similarly, when the temperature is very high, V will be very large
(since volume « temperature) or P will be very small and again PV = RT is obtained. Thus, at
extremely low pressures and high temperatures, all real gases obey the ideal gas laws.
(iv) At ordinary (medium) pressure: We have seen that at ordinary temperature, the
factor + predominates at low pressure, whereas the factor Pb predominates at high pressures
Vv
Therefore, these two factors will balance cach other at some intermediate range of pressures
in which the gas will show the ideal behaviour,
Thus at medium pressure, Pb=< 400 CONCEPTUAL ENGINEERING CHEMIstry
The equation (3.3) is reduced to. PV = RT= P’ V’
and the gas behaves like an ideal gas.
(¥) At high temperature: At high temperatures, V is very large and hence both Ph
and < will be negligibly small, so that we have PV = RT =P’ V"
Lc., at high temperatures the behaviour of a real gas nearly a;
grees With that expected
for ideal gas
(vi) At low temperature: Both P and V are small, hence, both pressure (attraction)
and volume corrections are appreciable, with the result that the deviations are more pronounced
(vii) Exceptional behaviour of hydrogen and helium: The molecules of these gases
are of very small mass and conscquently the force of attraction between the molecules is
always negligible.
Thus neglecting the term 7 the equation (3.3) is reduced to
PV- Pb =RT=P'V'
PV =P'V'+ Pb
ie, the product PV is greater than P’ V’ even at low pressures.
Solved Numerical Problems
Example 1. Using Van der Wall’s equation, calculate the pressure exerted by one
mole of carbon dioxide. When it occupies a volume of 0.05 litre at 100°C, given that
= 3.592, b = 0.0426 and R = 0.0821 litre atmosphere/ degree mole.
Solution. It is given that, n = one mole, V=0.05 litre
= 3.592 atms. litre? / mole? ,
5 = 0.0426 litre/ mole
R = 0.0821 litre atmosphere/ degree / mole
T= 100°C + 273 = 373°A.
Van der Waal's equation, for one mole
(? + Se) (v-0= RT
a _ RT
+ ak INTERMOLECULAR FORCES AND POTENTIAL ENERGY SURFACES 161
Substituting the values of a, 6, Vand T in the Van der Waal's equation,
20821373 _ 3.592. _ 701.5 amt
0.0: 0426 0.002:
Example 2, Two moles of ammonia are enclosed in a five litre flask at 27°C. Calculate
the pressure exerted by the gas assuming that
(i) the gas behaves like an ideal gas
(ii) the gas behaves like an real gas.
Solution. It is given that, V=S litres,
@ = 4.17 atms litre? mol?
4 = 0,037 litre mol! ,
R = 0.082 litre atoms. degree™! mol!
T=27+273 =300K,
Number of moles (71)
(i) When the gas behaves like an ideal gas, we have
PV =nRT
nRT _ 2X0.082%300 _ 9 94 am
Vv 5
(ii) When the gas behaves like an real gas, we apply Van der Waal's equation
2
(+2) (V-nb)=n RT (for m moles)
Vv
2
ie, pe BRT _ an?
7 “V=nb- v2
Substituting the values of a, b, R, V and T in above equation
_ 20.082%300_ 4.17% 22
© 5=2x0.037 5x5
P = 9,99 - 0.67 = 9.32 atm
3.8 ISOTHERMS OF CARBON DIOXIDE - CRITICAL PHENOMENON
The curves representing the variation of volume and Pressure at constant temperature
are called isotherms (Greek; iso ~ 'equal’). In the case of an ideal gas, the isotherms would
be rectangular hyperbolas
In 1869, T. Andrews studied the effect of pressure on volume of CO, at different
temperatures. When the volume readings were plotted against the pressure, a set of curves of
the type shown in Fig, 3.11 was obtained. Each curve corresponds to one particular temperature
_ a 162 CONCEPTUAL ENGINEERING CHEMIsTRY
and is, therefore, called isotherm. The curves should be rectangular, hyperbolas like that expected
for an ideal gas. It is quite clear that CO, does not give rectangular hyperbolas although with
increasing temperature the curves approximate to one. Let us consider the various isotherms
separately.
(i) Isotherm at 0°C: The isotherm shows that
carbon dioxide is entirely gaseous at low
Pressures and the volume decreases with in
creasing pressure in the normal fashion
Critical Point
Volume
Fig. 3.11. Andrews isotherms of CO, at different temperatures
(ii) Isotherm below 31°C: The isotherm below 31
the isotherm of 21°C, the point A correspond:
Pressure. At low pressures, if the
by the curve AB.
°C is not continuous. For example, in
Is to gaseous CO, occupying a certain
Pressure is increased, the volume decrease as indicated
At B liquefaction commences; vape
greater density and the decreases suddenl:
less than that of BC is approxi.
decrease in volume taking pla
our is converted into liquid of very much
y as the volume occupied by a liquid is much
-mately parallel to the volume axis indicating the sudden
ce at the same pressure,
Liquefaction is complete at C and CD shows the small effect of pressure on a
liquid. The steep line CD which is almost vertical Tepresents the compressibility of a
liquid and shows that the liquids are much less compressible, i.e., increase in pressure
produces a very small decrease in volume.
To summarize, along curve AB there is only y.
along BC liquid and vapour co-exists. Since BC is par
be only one pressure at which liquid and v;
pressure of the gas.
apour, along CD only liquid and
allel to the volume axis. there can
‘pour co-exits, This pressure is called vapout INTERMOLECULAR FORCES AND POTENTIAL ENERGY SURFACES wu
(iii) Isotherm at 31°C: As the temperature is raised, this horizontal portion becomes less
and less till at 31.1°C: it reduces almost to a point F, Above this temperature, there 1s no
trace of horizontal portion, i.e., beyond 31.1°C, there is no indication of liquefaction at
all. Point F is the critical point for CO. The distinction between liquid and vapour state
disappears at this point and CO, exits in a state called the critical state. The isotherm
passing through critical point is called the critical isotherm.
(iv) Isotherm above 31°C: If the temperature was beyond 31.1 °C,CO, could not be
liquefied. Yet Andrew's applied a pressure of 300-400 atm. However, at 21°C, only a
pressure of 75 atm was quite sufficient to liquefy CO.
From the experiment, Andrews concluded that if the temperature of CO, is above
31.1 °C, it cannot be liquefied no matter how high the pressure may be. This maximum
temperature (31.1°C) at which liquefaction can be brought about is called critical temperature.
The pressure required to liquefy a gas at the critical temperature is known as the critical
pressure. If the temperature happens to be below the critical temperature, the gas will liquefy
at a somewhat lower pressure. All other gases have been found to behave similarly. The critical
phenomenon observed by Andrews for CO, may be observed for any gas.
3.9 _ PRICINCIPLE OF CONTINUITY OF STATES
Let us refer back to the isotherms plotted in Fig.3.11 The dome-shaped curve shown by
the dashed line connects the end points of the horizontal portions of the isotherms. Since a
horizontal portion represents two phases in equilibrium, all points inside the dome correspond to
equilibrium between liquid and vapour. For such points, it is always possible to draw any sharp
distinction between liquid and vapour, since there is a definite boundary surface between the
two phases. For points lying outside the dome, only one phase (liquid or vapour) is present, and
here it is not possible to draw any sharp distinction between liquid and vapour.
Actually there is no dividing line between the liquid and the gaseous states and there is
a gradual transition from gas to liquid and vice versa without any abrupt change in state. The
fact that it is not possible to make distinction between a gas and a liquid is known as the
principle of continuity of state. The distinction between gas and liquid is possible only within
the dome area when both are present in equilibrium and there is boundary surface. In the
absence of this boundary, no fundamental distinction between gas and liquid is possible.
‘When a gas is compressed at a temperature below its critical temperature, its volume is
decreased, i.c., the free space between the molecules is decreased and the inter-molecular
forces are increased. Consequently, the gascous state changes to the liquid state, Therefore,
the liquid state is only a continuation of the gaseous state into a region of low volume
and high inter-molecular forces of attraction. Below the critical temperature whenever
Gaseous state is changed to liquid state, we have to pass through a stage when both the liquid
and the gaseous states change into liquid state and vice versa without passing through a stage
in which both the phases are present together,
In this transition, the continuity of state is said to be maintained. This can be done as
follows. Consider a certain volume of CO, gas represented by a first point P on the isotherm. 7 CONCEPTUAL ENGINEERING CHEMISTRY
Let us increase the pressure of the gas at constant volume from point P to point Q by Increasing
the temperature. After arriving at point Q, the volume is decreased at constant pressure along
the line QR by decreasing the temperature. At R, the temperature is again 31.1°C, but co,
exists as liquid; there has never been more than one phase present at any time. The volume of
the gas decreases gradually, as the temperature is decreased from Q to R. Ultimately, th.
molecules are so close that the inter-molecular forces of attraction become strong enough to
cause their condensation into the liquid state. Thus, it is not always possible to distinguish a gas
from a liquid and the conversion of gas to liquid or vice-versa is continuous. Therefore, the
liquid state may be taken as highly compressed gaseous state.
3.10 CRITICAL CONSTANTS
(i) Critical temperature of a gas (T.) is the minimum temperature which must be reached
before the gas can be liquefied by the application of pressure. A gas cannot be liquefied
by pressure above its critical temperature, no matter how high the applied pressure
may be. Each gas has a definite critical temperature, ¢.g., T, of CO, is 31.1 °C ot
304.1 K.
(ii) Critical pressure of gas (P.) is the minimum pressure necessary for the liquefaction
of a gas at critical temperature, e.g., P, for CO, is 72.9 atm.
Gii) Critical volume of a gas (¥.) is the volume occupied by one mole of the gas or liquid
under critical pressure and under critical temperature e.g. V, for CO» is 95.65 ml.
From Andrews experiment, very useful conditions for the liquefaction of a gas may be
stated as:
(a) The temperature must be at or below the critical temperature
(b) A suitable pressure must be applied equal to the critical pressure if the temperature
is at the critical temperature but becoming less if the temperature is reduced below
this value.
3.10.1 Relations Between van der Waals’ Constants and Critical Constants
A very good confirmation of the general character of Van der Waals equation is furnished
by its application to critical phenomenon.
The Van der Waals’ equation is
a .
G + 5) (V-6)= RT (putting n=1)
a ab
Alternatively, PV + ve Pb- ae =RT
Multiplying throughout by V2, we get
PV3 + aV ~ PbY?- ab = RTV? INTERMOLECULAR FORCES AND POTENTIALENERGY ‘SURFACES 166
PV3 + aV ~ PbY? - ab ~ RTV2 = 0
Arranging in descending powers of V
PV3 ~ PbV? - RIV? 4 aV ~ ab = 0
Dividing by P, we get
2
vi-py2- RIV" aV ab og
Pr P
vi-ve(5e8T) ev oo G4)
This is a third-degree equation in terms of V (cubic cquation in V) and below a certain
value of temperature T, the equation can have three real roots. With the rise of temperature,
these roots approach one another and become identical ultimately. This can be easily understood
if we plot a theoretical P- V_ graph from the Van der Waals’ cquation. The curves obtained
are of the type ABLMNCD as shown in the Fig. 3.12.
The three real unequal roots correspond to point B, M and C. The points B and C
represent saturated vapour and liquid, respectively, but M has no physical sigiificance. As the
temperature rises, the S-shaped dotted portion of the curve gets reduced to a point. The values
for the volume of liquid and gas approach each other until at this point, the three values of V
become identical. This point corresponds to the critical temperature and the volume V. At the
critical point, then the three roots of the Van der Waals’ equation become identical and equal
toV.
Since this is the value of the three roots of the Van der Waals' equation at the critical
point,
Critical Point
Nadu
Fig. 3.12. Isotherms of CO, from Van der Waals’ equation CONCEPTUAL ENGINEERING CHEMistry
466
(V-Vv.P=0
or V3-3 V, V243V2V- Ve=0 4
Under critical conditions, T= T and P = P,
Substituting these values in equation (3.4),
-(3.6)
‘As both the (3.5) and (3.6) are identical, then. the coefficients of the equal powers of V
in the two equations may be equated as
RT,
3V, =b+—*
le P 3.7
3v;=2 3
aan -(3.8)
2 _ab
vie2 3
c P, (3.9)
Dividing equation (3.9) by equation (3.8), we get
Wwe g %
3V2 P. 3
or V,=36
-(3.10)
Substituting the value of V from equation (3.4) in equation (3.2), we get
a
oat
<=3 =27b
P x (3b)
a
or 7 (3.11)
Substituting the values of V, and P, in equation (3.1), we get
3x3b=b+RTx or 9b =b4 RT x
a © a
2767
of = 86= RT, x on T,=8x—o xt
4 276? R
8a
Alternatively,
27bR
(3.12) INTERMOLECULAR FORCES AND POTENTIAL ENERGY SURFACES 167
3
3.10.2 Derivation of P.V. = a RT, from Van der Waal's Equation
From Van der Waal's equation, we have
wovi(seRk)s
(3.13)
©
Inaddition, = V\- 3. V, VE + 3V2V- V3=0 v.14)
Equating the coefficients of equation (3.13) and (3.14), we get
RT,
= f+b 5
P, (3.15)
(3.16)
(3.17)
3 1
v, =3b or b=5N, (3.18)
Substituting the values of b in equation (3.15), we get
V. _ RT,
3V.--£ £
or 3
or or
or (3.19)
3.10.3 Calculation of Van der Waal's Constants in terms of T. and P_
Rearranging equatino (3.19), we get
vat
ei?
Squaring, we get
a P, (3.20) CONCEPTUAL ENGINEERING CHEMISTRY
168
a, i i
Substiting the value of V: P. from equation (3.16) in equation (3.20), we get
+(3.21)
Substiting the value of V_ = 34 in equation (3.15), we get
RT,
or
or
(3.22)
3.11__POTENTIAL ENERGY SURFACE
potential energy surface describes the energy of a system, particularly a collection of
atoms in terms of the positions of the atoms. The surface might define the energy as a function
of one or more coordinates; if there is only one coordinate, the surface is called a potential
energy curve or energy profile.
For a system with two degrees of freedom (e.g. two bond lengths), the value of the
energy is a function of two coordinates with Tespect to position.
af %G=H-O-HBond Angle
J 0ase
Fig. 3.13, Potential energy surface for water molecule: Shows the energy minimum
Corresponding to optimized molecular structure for water, O-H bony length
of 0.0958nm and H-O-H bond angle of 104.5*,
™ |
INTERMOLECULAR FORCES AND POTENTIAL ENERGY SURFACES 169
The potential energy surface concept finds application in many fields such as chemistry
and physics. It can be used to theoretically explore properties of structures composed of atoms.
For example, finding the minimum energy, shape of a molecule or ealculating the rates of a
chemical reaction.
In mathematics, the geometry of a set of atoms can be described by a vector, 7, whose
=
elements represent the atom positions. The vector
of the atoms, or could also be a set of inter-atomic distances and angles,
> > >
When + is given, the energy as a function of the positions, E(7r), is the value of Er)
for all r of interest. E gives the height on the "energy diagram"
so that the concept of a
potential energy surface becomes usful
To study a chemical reaction using the Potential Energy Surface (PES) as a function of
atomic positions, it is necessary to calculate the energy for every atomic arrangement of interest.
Methods of calculating the energy of
a particular atomic arrangement of atoms are evaluated
by applying computational chemistry.
For simple chemical systems like H, the information about inter-atomic interactions,
can be obtained from an analytically derived expression for the enerey as a function of the
atomic positions. An example is the London-Eyring-Polanyi-Sato potential for the system
H + Hy as a function of the three H-H distances
Application
points (Or points with a zero gradient) have physical meaning ic. energy minima correspond to
Physically stable chemical species and saddle points correspond to transition states, the highest
energy point on the reaction coordinate,
(which is the lowest energy pathway connecting a
chemical reactant to a chemical product).
Classification of PES
The bond length extension for the newly formed A — B bond is given as
Rap = Rap - Rap
where Ryp is the A~B bond length in the transition state and
Rig is that bond of the product molecule.
_—_———e 1 CONCEPTUAL ENGINEERING CHEMIstay
Similarly, for the bond which is broken in the reaction, Ric = Rac - R&c, where Rye
refers to the reactant molecule.
For exothermic reactions, a PES is classified as attractive, if Rap > Ric, so that the
transition state is reached while the reactants are approaching each other. After the transition
state, the A-B bond length continues to :lecrease, so that much of the liberated reaction ener,
is converted into vibrational energy of the A-B bond. It means that extension in bond length in
the reaction molecule (Rp) must be greater than that of product molecule Ryo), the PES is
considered as attractive,
Let us consider an example of the reaction: K + Br, —» K-Br + Br, in which the initial
long-range attraction of the reactants leads to an activated complex resembling K*+++Br-++-Br.
The vibrationally excited populations of product molecules can be detected by infrared
chemiluminescence.
In contrast, the potential energy surface for the reaction H + Cl, + HCI + Cl is
repulsive, because R"}yc) < R"¢jcy and the transition state is reached when the products are
separating, For this reaction in which the atom H is lighter than Cl, and HCI, the reaction
energy is released primarily as translational kinetic energy of the products
For a reaction, such as F +H, — HF +H in which atom F is heavier than H and HF,
there is mixed energy release, both vibrational and translational, even though the potential energy
surface is repulsive.
For endothermic reactions, the type of surface determines the type of energy which is
most effective in bringing about reaction. Translational energy of the reactants is most effective
at inducing reactions with an attractive surface, while vibrational excitation is more effective
for reactions with a repulsive surface.
As an example of the latter case, the reaction F + HCI (v=1) — Cl + HF is about five
times faster than F + HCI(v = 0) — Cl + HF for the same total energy of HCI
3.11.1 Potential Energy Surface for H} system
The Hj ion has an important role to play in the chemistry interstellar space and it is
responsible for many important chemical reaction taking place in the medium. Hj is the most
abundant polyatomic ion found in the universe. Thus, it plays a significant role in astrochemistry
and astrophysics. Due to its simplicity, the system acts as a bench mark for high accuracy ab
initio molecular theory and kinetic reactions. The formation raction of Hj ion is given below:
Hj +H) > Hj+H
(3.23)
It can be achieved in the following three ways:
Hj +e +H) +H 3.24)
Hj+e 3 H+H+H (3.25)
Hy +e¢ > HJ +H (3.26) INTERMOLECULAR FORCES AND POTENTIAL ENERGY SURFACES m1
All the above four reactions (3.23), (3.24), (3.25) and (3,26) are very fast and the
fragile equilibrium between them determines the amount of H} in intersteller space. Thus, the
thermodynamic and kinetic study of the above said reaction is of vital importance.
The most important requirement for this study is the availability of very accurate and
complete Potential Energy Surface (PES) of Hj, which describes all the different channels
involved in the above mentiond reactions. The PES has to be calculated with accuracy in the
areas corresponding to the reactants, products as well as all the transition and intermediate
states of the reaction. These calculations are based on quantum chemistry and are quit difficult
for the students of this level to understand,
Many researchers are engaged in the study of potential energy surface for the Hj
molecule-ion and some other species such as HF, and HCN. etc. Although it is difficult to go
into the details of the research work, yet two potential energy surface diagrams are given
below.
Considerable progress in calculating the potential energy surface of Hj has been made.
A recent attempt in the direction has been made by Ludivik Adamowicz and Michele Pavanello
in their research paper published on October, 2012 in philosophical transaction the Royal
Society A. They adopted the most accurate electronic structure calculation using their functions
expansions in term of basis function dependent on the inter-clectron distances to calculate a
highly accurate potential energy surface for the H ion. The functions are explicity correlated
Gaussion function, which include inter-electron distances in the exponent.
They have implemented the computational procedures to calculate with highest
the total non-relativistic BO energy of small molecules, usin
is the most accurate global ground-state Hi PES available
Together wi
accuracy
ig FECG functions. At present this
ith a simple model for non-adiabatic effects, the calculated PES has enabled
to predict the vibrational transitions of H3 in the infrared and mid-visible regions of the spectrum
\with unpredecedented accuracy. Measurements extending far into the visible region have recently
become available, and these calculations have been shown to match those
observed through
spectrial lines with an average deviation as low as 0.14 cm-!
Solved Typical Problems
|
Problem 1. Define Van der waals forces. Discuss their nature.
Solution. The intermolecular attractive forces existing between all molecules when they are
close to one another called Van der waals forces. These forces are very weak is nature and
operate only when molecules are very close to one another, The attractive force is opposed by
two factors:
(i) The repulsive force between the electron clouds of the adjacent molecules
(ii) The repulsive force between the nuclei of near by atoms
However, the attractive forces overpower the repulsive forces. CONCEPTUAL ENGINEERING CHEMISTRY
172
Problem 2. What do you know about the origin of Van der Waals forces?
Solution, Imagine that the clectron distribution in a molecule becomes unsymmetrical and is
concentrated towards one side of the molecules . At this intance of time, a temporary dipole is
formed in this molecule. The nearby molecule Y is affected by this temporary dipole at the same
moment and its nucless is attracted towards the nagtive and of X. The natural attraction between
the nucleus of one molecule and the clectronic cloud of the molecule and repulsion between the
nuclei of the two approaching molecules and also repulsion between their electronic clouds
comes into operation. The change in one of the molecules may shift to the other side in the next
moment and this effect may be followed on other near by molecules. This results in the formation
of two new dipole oppositly oriented between the two nearest molecules. These nearly
instantancously fluctuating dipole result in an attractive force among the molecules of the
substance, which is referred to as Van der Waals weak attractive forces.
Problem 3. On what factors strength of intermolecular forces depend? How do these
forces affect the physical properties of the substances.
Solution. The strength of intermoleculars of forces depends upon the following factors.
(i) Size of the molecules i.¢ their molecular mass.
(ii) Number of electrons present in their molecules
ii) Molecular structure.
With increase in strength of these intermolccule of forces, the melting and boiling point
of the substances increase .
Problem 4. Compare the strength of intermolecular forces in H, and Halogens and
arrange them in increasesing order w.r.t. strength.
Solution. Hz being the smallest molecule, the strength of intermolecule forces among its
molecules would be the least. Among the halogens it would go on increasesing with increase in
their respective size which is directly related with their molecular a Mmasses,. So trend in the
variation of strength would follow the order as under:
H,
